EP1606429B1 - Verfahren zur cvd-abscheidung eines silberfilms auf einem substrat - Google Patents

Verfahren zur cvd-abscheidung eines silberfilms auf einem substrat Download PDF

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Publication number
EP1606429B1
EP1606429B1 EP04742294A EP04742294A EP1606429B1 EP 1606429 B1 EP1606429 B1 EP 1606429B1 EP 04742294 A EP04742294 A EP 04742294A EP 04742294 A EP04742294 A EP 04742294A EP 1606429 B1 EP1606429 B1 EP 1606429B1
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EP
European Patent Office
Prior art keywords
silver
substrate
process according
precursor
amine
Prior art date
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EP04742294A
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English (en)
French (fr)
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EP1606429A1 (de
Inventor
Jean-Manuel Decams
Hervé Guillon
Pascal Doppelt
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Qualiflow
Centre National de la Recherche Scientifique CNRS
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Qualiflow
Centre National de la Recherche Scientifique CNRS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds

Definitions

  • the present invention relates to the deposition of thin films of silver on various substrates, in particular on superconducting substrates.
  • the object of the present invention is to provide a method of depositing a silver layer on a substrate, by a suitable choice of reagents for the dissolution of a silver precursor in a solvent usable in CVD.
  • silver pivalate (CH 3 ) 3 -C-CO 2 Ag is particularly preferred. Its decomposition temperature is 200 ° C.
  • organic compounds which are liquid at room temperature and up to about 200 ° C under normal pressure conditions are preferred.
  • mesitylene cyclohexane
  • xylene xylene
  • toluene n-octane
  • the amine may be chosen from primary, secondary or tertiary monoamines, or from polyamines.
  • monoamines mention may be made of n-hexylamine, isobutylamine, disecbutylamine, triethylamine, benzylamine, ethanolamine and diisopropylamine.
  • polyamines include tetramethylethylenediamine.
  • the nitrile may be chosen from acetonitrile, valeronitrile, benzonitrile and propionitrile.
  • mixtures of mesitylene with n-hexylamine, isobutylamine, diisopropylamine, triethylamine, acetonitrile, benzonitrile or valeronitrile, mixtures of propionitrile with hexylamine, and the like are particularly preferred.
  • the substrate on which the silver layer is deposited can be a high-T c superconductor material, a dense ceramic or a porous ceramic, a heat resistant polymer, a glass, MgO, LaAlO 3, Ni, Si, GaAs, InP, SiC and SiGe.
  • the process makes it possible to obtain silver deposits having a thickness up to 800 nm.
  • the composition containing the silver precursor is sent to a vaporization device through which it is introduced into a high-temperature deposition chamber. which contains the support on which the silver layer must be deposited. Before its arrival in the vaporization device, the composition is generally maintained in a tank at room temperature.
  • the vaporization of the precursor composition can be carried out using various devices known to those skilled in the art. By way of a preferred example, mention may be made of the device described in Chem. Mast. 13, 3993 (2001) ), marketed by Jipelec under the name "InJect System for the injection and evaporation of pure liquid precursors or in the form of solutions”.
  • the temperature of the substrate to be coated and the temperature in the deposition chamber is between 200 and 450 ° C.
  • the deposition chamber is under an oxygen atmosphere or under an atmosphere of hydrogen and at a pressure less than or equal to 15 Torr. Hydrogen or oxygen may be introduced into the deposition chamber in the form of a mixture with N 2 in which the volume ratio H 2 / N 2 or O 2 / N 2 is less than or equal to 1.
  • a cold plasma may possibly be added around the support.
  • the support intended to receive the silver layer it is sufficient for the support intended to receive the silver layer to be kept at the same temperature that prevails in the evaporator.
  • the silver layer may be deposited on the support as a first layer or as an nth metallization layer for electronic devices requiring several levels of metallization.
  • the support may be constituted by one of the aforementioned materials taken as such, or by one of these materials carrying one or more intermediate layers.
  • intermediate layers include metal films (for example a Ni film), an organic layer (for example a layer of a polymer material), or diffusion layers consisting of for example, TiN, TiSiN, Ta, TaN, TaSiN, WN and WSiN.
  • the thickness of the silver layer that is deposited on the support depends on the concentration of the precursor composition, the flow rate of this composition during the passage into the vaporization device, the duration of the vaporization, the respective temperatures in the the reactor and on the support. In general, less concentrated compositions and / or lower flow rates for obtaining thin layers, and more concentrated compositions and / or higher flow rates for obtaining thick layers are used.
  • thin layer is generally meant a layer having a thickness of less than or equal to 50 nm, called the nucleation layer.
  • thick layer is generally meant a layer having a thickness between 50 nm and 1 micron.
  • compositions can be used in a solvent with a high dissolution coefficient at a precursor concentration close to saturation.
  • concentration must remain below the saturation value, in order to avoid the reprecipitation of the precursor which would have the effect of hindering the vaporization.
  • the implementation of the method of the invention for the deposition of silver layers by CVD makes it possible to obtain silver layers of good quality having a good adhesion to the support on which they are deposited.
  • the examples were carried out using a CVD reactor constituted by a device “InJect” supra, coupled to a chemical vapor deposition chamber.
  • Said device “InJect” comprises four main parts: the storage tank of the solution, an injector connected by a supply line to the storage tank and provided with an electronic control device, a carrier gas supply line or neutral carrier (for example nitrogen) and an evaporator.
  • the chemical vapor deposition chamber which contains the substrate to be coated, comprises heating means, an oxygen supply or hydrogen, and pumping means and reducing pressure.
  • the evaporator is connected to the chemical vapor deposition chamber by a pipe which is provided with heating means and which is kept at the same temperature as the evaporator.
  • the chemical vapor deposition chamber and the substrate to be coated placed therein are maintained at a temperature higher than that of the evaporator.
  • the silver precursor solution is introduced into the tank maintained at a pressure of 1 bar, and then propelled from said tank through the injector by pressure difference in the evaporator which is kept under vacuum.
  • the injection rate is controlled by the injector which can be considered as a micro-solenoid valve and which is controlled by a computer.
  • a silver film was deposited on a substrate placed in the enclosure deposition at 250 ° C under a pressure of 7.5 Torr.
  • FIGS. 1a and 1b show the Scanning Electron Microscopy (SEM) images of the surface of the Ag deposition obtained on the MgO substrate at different magnifications.
  • FIGS. 2a and 2b show Scanning Electron Microscopy (SEM) photographs of the surface of the Ag deposition obtained on the LaAlO 3 substrate under different magnifications.
  • FIG. 3 represents the X-ray diffraction pattern of the deposit obtained on the monocrystalline MgO substrate.
  • N represents the number of shots, in arbitrary units.
  • 2 ⁇ represents the diffraction angle, in degrees.
  • Example 2 The procedure described in Example 1 was repeated, replacing the diisopropylamine with n-hexylamine, respectively with a monocrystalline substrate of MgO, and with a monocrystalline LaAlO 3 substrate.
  • a silver film was deposited on a monocrystalline Si substrate maintained at 300 ° C and placed in the deposition chamber at 150 ° C under a pressure of 7.5 Torr.
  • a silver film having a thickness of 250 nm was deposited in 35 minutes, with a growth rate of 0.43 ⁇ m / h.
  • a silver film was deposited on a substrate maintained at 320 ° C. and placed in the deposit enclosure at 150 ° C. under a pressure of 7.5 Torr.
  • Two samples were prepared according to this method, one with Si monocrystalline substrate, the other with SiO 2 / Si substrate.
  • a silver film having a thickness of 150 nm was deposited in 8 minutes, with a growth rate of 1.125 microns / h.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Claims (10)

  1. Verfahren zur Abscheidung eines Silberfilms auf einem Substrat, das darin besteht, eine Silberabscheidung mittels CVD auf dem Substrat unter Einsatz einer Silbervorläuferlösung durchzuführen, wobei:
    - der Silbervorläufer ein Silbercarboxylat RCO2Ag ist, worin R ein unverzweigter oder verzweigter Alkylrest mit 3 bis 7 Kohlenstoffatomen ist, das in Form einer Lösung in einer organischen Flüssigkeit eingesetzt wird;
    - die Konzentration des Vorläufers in der Lösung zwischen 0,01 und 0,6 mol/l beträgt und unter der Sättigungskonzentration bleibt;
    - die organische Flüssigkeit ein Amin und/oder ein Nitril umfasst, sowie gegebenenfalls ein Lösungsmittel, dessen Verdampfungstemperatur niedriger ist als die Zersetzungstemperatur des Vorläufers;
    - der Volumsprozentsatz des Amins und/oder Nitrils in der organischen Flüssigkeit mehr als 0,1 % beträgt;
    wobei das Verfahren dadurch gekennzeichnet ist, dass es unter Sauerstoff- oder Wasserstoffatmosphäre durchgeführt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Silbervorläufer Silberpivalat (CH3)3-C-CO2Ag ist.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Lösungsmittel eine organische Verbindung ist, die bei Raumtemperatur bis etwa 200 °C unter Normaldruckbedingungen flüssig ist.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass das Lösungsmittel aus Mesitylen, Cyclohexan, Xylol, Toluol und n-Octan ausgewählt wird.
  5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Amin ein Monoamin, ausgewählt aus n-Hexylamin, Isobutylamin, Di-sec-butylamin, Triethylamin, Benzylamin, Ethanolamin und Diisopropylamin ist.
  6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Amin ein Polyamin ist.
  7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Nitril aus Acetonitril, Valeronitril, Benzonitril und Propionitril ausgewählt wird.
  8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Substrat aus einem Material besteht, das aus supraleitenden Materialien mit hoher Tc, Keramiken, wärmebeständigen Polymeren, Gläsern, MgO, LaAlO3, Ni, Si, AsGa, InP, SiC und SiGe ausgewählt wird.
  9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Temperatur des zu beschichtenden Substrats zwischen 200 und 450 °C beträgt.
  10. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass ein Kaltplasma rund um das Substrat zugesetzt wird.
EP04742294A 2003-03-25 2004-03-19 Verfahren zur cvd-abscheidung eines silberfilms auf einem substrat Expired - Lifetime EP1606429B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0303613 2003-03-25
FR0303613A FR2852971B1 (fr) 2003-03-25 2003-03-25 Procede pour le depot par cvd d'un film d'argent sur un substrat
PCT/FR2004/000678 WO2004087988A1 (fr) 2003-03-25 2004-03-19 Procede pour le depot par cvd d'un film d'argent sur un substrat

Publications (2)

Publication Number Publication Date
EP1606429A1 EP1606429A1 (de) 2005-12-21
EP1606429B1 true EP1606429B1 (de) 2007-12-26

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EP04742294A Expired - Lifetime EP1606429B1 (de) 2003-03-25 2004-03-19 Verfahren zur cvd-abscheidung eines silberfilms auf einem substrat

Country Status (6)

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US (1) US7608299B2 (de)
EP (1) EP1606429B1 (de)
AT (1) ATE382105T1 (de)
DE (1) DE602004010894T2 (de)
FR (1) FR2852971B1 (de)
WO (1) WO2004087988A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008030900A1 (de) * 2008-06-30 2009-12-31 Oliver Feddersen-Clausen Verdampfbare Silbercarboxylat-Amin-Komplexe als Silberprecursor sowie Verdampfungsverfahren für dieselben

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2880036B1 (fr) * 2004-12-23 2007-09-07 Commissariat Energie Atomique Procede de preparation de nonoparticules d'argent ou d'alliage d'argent dispersees sur un substrat par depot chimique en phase vapeur
FR2887560B1 (fr) * 2005-06-28 2007-10-12 Commissariat Energie Atomique Films composites a base de metal et d'oxyde pour applications antimicrobiennes et procede de protection ou de decontamination d'un substrat mettant en oeuvre de tels films
FR2919308B1 (fr) * 2007-07-23 2009-12-11 Commissariat Energie Atomique Procede de preparation d'un materiau nanocomposite par depot chimique en phase vapeur.
GB0812483D0 (en) * 2008-07-08 2009-01-07 Bae Systems Plc Electrical Circuit Assemblies and Structural Components Incorporating same
CN102633326B (zh) * 2012-04-28 2014-05-21 云南铜业股份有限公司 处理铜冶金流程中含氯酸性废水的离子交换膜电解方法
FR3062327B1 (fr) * 2017-01-30 2019-04-19 Safran Aircraft Engines Procede pour le decollement d'un element metallique colle a un element en materiau composite
FR3129611A1 (fr) 2021-11-29 2023-06-02 IFP Energies Nouvelles Catalyseur d’hydrocraquage comprenant une zeolithe y specifique pour la production de naphta
FR3130641A1 (fr) 2021-12-16 2023-06-23 IFP Energies Nouvelles Catalyseur d’hydrocraquage comprenant une zeolithe y specifique et une zeolithe de type mfi pour la production d’une charge de vapocraquage
FR3133389A1 (fr) 2022-03-08 2023-09-15 IFP Energies Nouvelles Catalyseur d’hydrocraquage comprenant deux zeolithes y dont une zeolithe y specifique pour la production de naphta

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
DE3344343A1 (de) * 1983-12-08 1985-06-13 Battelle-Institut E.V., 6000 Frankfurt Verfahren zur herstellung von schalenkatalysatoren
JPH0940489A (ja) * 1995-03-30 1997-02-10 Pioneer Electron Corp Ｍｏｃｖｄの固体原料供給方法及び供給装置
US20020041928A1 (en) * 1997-03-26 2002-04-11 Leonid V. Budaragin Method for coating substrate with metal oxide coating
US6010969A (en) * 1996-10-02 2000-01-04 Micron Technology, Inc. Method of depositing films on semiconductor devices by using carboxylate complexes
US6267074B1 (en) * 1997-02-24 2001-07-31 Foi Corporation Plasma treatment systems
US6613924B1 (en) * 1999-11-23 2003-09-02 Research Foundation Of State Of New York Silver precursors for CVD processes
JP2005511894A (ja) * 2001-12-04 2005-04-28 プライマックス・インコーポレーテッド 化学蒸着用ベーパライザ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008030900A1 (de) * 2008-06-30 2009-12-31 Oliver Feddersen-Clausen Verdampfbare Silbercarboxylat-Amin-Komplexe als Silberprecursor sowie Verdampfungsverfahren für dieselben
DE102008030900B4 (de) * 2008-06-30 2011-01-13 Oliver Feddersen-Clausen Verdampfbare Silbercarboxylat-Amin-Komplexe als Silberprecursor sowie Verdampfungsverfahren für dieselben

Also Published As

Publication number Publication date
DE602004010894T2 (de) 2008-12-18
FR2852971B1 (fr) 2005-06-03
US20070148345A1 (en) 2007-06-28
WO2004087988A1 (fr) 2004-10-14
FR2852971A1 (fr) 2004-10-01
EP1606429A1 (de) 2005-12-21
ATE382105T1 (de) 2008-01-15
US7608299B2 (en) 2009-10-27
DE602004010894D1 (de) 2008-02-07

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